Acrylic polymer compositions with crystalline side chains and processes for their preparation

ABSTRACT

Acrylic polymer compositions with crystalline side chains are disclosed. Solution polymerization, aqueous suspension polymerization, and aqueous dispersion polymerization processes for the preparation of the acrylic polymer compositions with crystalline side chains are also disclosed. Methods of use for the acrylic polymer compositions with crystalline side chains, including dry powder coatings; wax replacements in floor polishes and wood coatings; nonwoven and textile coatings; adhesives; and hot melt adhesives are also disclosed.

This is a divisional application of U.S. application Ser. No.09/388,882, filed Sep. 2, 1999, now U.S. Pat. No. 6,437,070, whichclaims the benefit of Provisional application Ser. No. 60/101,415, filedSep. 22, 1998.

Acrylic polymers have many useful properties such as durability,flexibility in composition and glass transition temperature (“Tg”),weather resistance, adhesion to polar substrates, and compatibility withmany polar polymers and inoganic components. While each of theproperties may be desirable, it is difficult to obtain all of them inone polymer. One often needs to sacrifice one property to gain anotherbecause the properties of the polymer depend on the polymer'scomposition, molecular weight, and Tg. For example, a low Tg may bedesirable for a polymer composition which would be useful in adhesiveapplications, but the low Tg polymer may not provide good durability.

In addition, because acrylic polymers are generally amorphous, they arenot effective in all applications where crystallinity is desired. Theydo not adhere well to most non-polar substrates such as polyolefins.Amorphous acrylic polymers also are inferior in terms of waterresistance and durability as compared with polyolefins. Therefore, thereis a need for low cost polymer compositions which provide durability,flexibility in composition and Tg, weather resistance, adhesion to polarand non-polar substrates, compatibility with polar polymers and inoganiccomponents, and water resistance.

Previous methods to achieve a combination of desired properties ofacrylic polymers and olefin polymers in “one” polymer includedphysically mixing an acrylic polymer and an olefin polymer orcopolymerizing an olefin monomer and an acrylic monomer. These methodshave not been successful. Physical mixing of acrylic polymers andpolyolefins does not usually yield useful compositions because the twopolymers are incompatibile. Copolymerizing an olefin monomer and anacrylic monomer is difficult because there is poor reactivity betweenthe two monomers. In addition, copolymerization of two monomers usuallyresults in a composition with an average of the combined properties ofeach homopolymer rather than enhanced properties.

U.S. Pat. No. 5,387,450 ('450) tries to solve the problem. This patentdiscloses polymer compositions which contain as polymerized unitscrystallizable side chain monomers and are useful as adhesives. Belowthe melting temperature of the crystallizable side chain, the polymer isnon-tacky. Above the melting temperature of the crystallizable sidechain, the polymer turns into a tacky adhesive. The compositions arerequired to contain at least 50 weight percent of a crystallizable sidechain monomer. The crystallizable side chain monomers are acrylates ormethacrylates with 14 to 22 carbon atoms as side chains. Even thoughthis patent provides a route to achieve some of the properties discussedabove, there are still several problems unresolved by the patent. Thecrystallizable side chain monomers of the patent have lower meltingpoints and are more soluble in organic solvents than crystallizable sidechain monomers with more carbon atoms in the side chains. Therefore, oneproblem is that the patent does not address how to processcrystallizable side chain monomers with more carbon atoms in the sidechains, which require higher temperatures to melt and are less solublein organic solvents. Another problem is that crystallizable side chainmonomers are relatively new and due to their special structure areestimated to cost several times more than the other monomericcomponents. For these reasons, it is desirable to minimize the amount ofcrystallizable side chain monomer in one polymer and still achieve theproperties described above. Despite the disclosure of '450, there isstill a need for low cost polymer compositions which provide durability,flexibility in composition and Tg, weather resistance, adhesion to polarand non-polar substrates, compatibility with polar polymers and inoganiccomponents, and water resistance.

To provide the desired polymer compositions, the inventors have preparedpolymers containing an acrylic backbone with less than 50 percent byweight synthetic wax monomer (“SWM”). The SWM contains crystallinepolyethylene side chains and therefore is a crystallizable side chainmonomer. One benefit from the copolymers of this invention is that onemay achieve physical crosslinking through the association of one polymercomponent. This association can be crystallization or simply phaseseparation. The physical crosslinks that form are not permanent and canbe “decrosslinked” by heating. Through such physical crosslinking, thebackbone polymer matrix forms a network like structure, yet it can befully decrosslinked when the polymer is heated above the meltingtemperature of the association blocks. Formation of a network structurehelps to prevent loss of the physical properties when one has to reducethe molecular weight or Tg of the backbone polymer for processing orflexibility reasons.

In a first aspect, the present invention provides a polymer including aspolymerized units:

A) from 1 to less than 50 percent by weight of a synthetic wax monomerof formula I:

wherein

R₁ is selected from H and CH₃,

R₂is selected from H and C₁-C₅ alkyl,

R₃ is selected from H and CH₃,

n=9-115, preferably 12-90, more preferably 15-50, and

m=0-1370, preferably 0-65, more preferably 0-50; and

B) from 50 to 99 percent by weight of at least one second monomer.

Previously, it has been difficult to prepare the polymer compositionsdescribed above. For example, the '450 patent described above utilized aone shot solution polymerization reaction to polymerize the monomers.For a solution process, it is desirable to be able to gradually add theSWM to the polymerization kettle because it is believed that the SWMwill be more evenly incorporated into the polymer. Emulsion andsuspension processes are desirable because they allow for a reduction ofor elimination of organic solvents. The '450 patent did not addressthese concerns. Consequently, there is a continuing need for processesto prepare polymers containing SWMs.

The inventors have provided several approaches to preparing polymerscontaining SWMs. In one approach, a SWM slurry is prepared prior topolymerization of the SWM. The slurry may be used to prepare solution orsuspension polymers. For a solution process, the slurry may be combinedwith additional monomers or organic solvent and co-fed to a reactor withan initiator. For a suspension process, the slurry is combined with aninitiator and an aqueous solution and polymerized.

In a second aspect, the present invention provides a method of preparinga polymer from a slurry by: 1) forming a slurry by cooling a solutioncontaining a synthetic wax monomer and a solvent; 2) forming a reactionmixture by admixing at least one second monomer with the slurry; and 3)polymerizing the reaction mixture in the presence of an initiator.

In a third aspect, the present invention provides a method of preparinga polymer from an emulsion by dissolving a synthetic wax monomer in atleast one second monomer to form a solution, admixing water and at leastone surfactant to provide a second solution, forming a monomer emulsionby admixing the first and second solutions, providing a reactor withheated water, and polymerizing the monomer emulsion by adding themonomer emulsion and at least one initiator to the reactor.

In a fourth aspect, the present invention provides a method of coatingincluding applying a composition containing the polymer of the inventionto a substrate.

As used throughout this specification, by the term (meth)acrylic acid ismeant both acrylic acid and methacrylic acid. Likewise, as usedthroughout this specification, by the term (meth)acrylate is meant bothacrylate and methacrylate esters.

The SWMs of this invention are C₂₄ to C₈₀, preferably C₃₀ to C₅₀ethylenically unsaturated (meth)acrylate monomers or ethoxylates thereofand are formed from C₂₄ to C₈₀ synthetic wax alcohols. Generally, theSWMs are formed by reacting a C₂₄ to C₈₀ synthetic wax alcohol orethoxylate thereof with an alkyl (meth)acrylate in the presence of azirconium catalyst and suitable inhibitor, although they may be made byother processes well known in the art. Suitable alcohols or ethoxylatesare available from Baker Petrolite, Inc. Houston, Tex. as Unilin™ orUnithox™ products. Suitable examples of SWMs include the acrylate ormethacrylate esters of Unilin 350, Unilin 450, Unilin 550, Unilin 700,and Unithox 450. The amount of SWM in the polymer is typically from 1%to less than 50%, preferably 3% to 45%, more preferably 4% to 40%, mostpreferably 5% to 35% by weight, based on the total weight of the polymerof this invention.

The at least one second monomer may be an ethylenically unsaturatedmonomer. Suitable ethylenically unsaturated monomers include acrylic andmethacrylic acid and esters thereof. Generally, the (meth)acrylates areC₁ to C₂₄ (meth)acrylates. The (meth)acrylate is typically from 50% to99%, preferably 55% to 97%, more preferably 60% to 96% by weight, basedon the total weight of the polymer of the composition of this invention.Examples of the alkyl (meth)acrylate are methyl methacrylate (MMA),ethyl methacrylate (EMA), methyl and ethyl acrylate, propylmethacrylate, butyl methacrylate (BMA) and acrylate (BA), isobutylmethacrylate (IBMA), hexyl and cyclohexyl methacrylate, cyclohexylacrylate, 2-ethylhexyl acrylate (EHA), 2-ethylhexyl meth-acrylate, octylmethacrylate, decyl methacrylate, isodecyl methacrylate (IDMA, based onbranched (C₁₀)alkyl isomer mixture), undecyl methacrylate, dodecylmethacrylate (also known as lauryl methacrylate), tridecyl methacrylate,tetradecyl methacrylate (also known as myristyl methacrylate),pentadecyl methacrylate, dodecyl-pentadecyl methacrylate (DPMA), amixture of linear and branched isomers of dodecyl, tridecyl, tetradecyland pentadecyl methacrylates; and lauryl-myristyl methacrylate (LMA), amixture of dodecyl and tetradecyl methacrylates, hexadecyl methacrylate,heptadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate,cosyl methacrylate, eicosyl methacrylate, cetyl-eicosyl methacrylate(CEMA), a mixture of hexadecyl, octadecyl, cosyl and eicosylmethacrylate; and cetyl-stearyl methacrylate (SMA), and a mixture ofhexadecyl and octadecyl methacrylate. Mixtures of one or more(meth)acrylates may also be used.

Another class of suitable ethylenically unsaturated monomers useful asthe at least one second monomer are vinylaromatic monomers whichinclude, among others, styrene (Sty), α-methylstyrene,-vinyltoluene,p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylenes, andthe like. The vinylaromatic monomers can also include theircorresponding substituted counterparts, such as halogenated derivatives,i.e., containing one or more halogen groups, such as fluorine, chlorineor bromine; and nitro, cyano, alkoxy, haloalkyl, carbalkoxy, carboxy,amino, alkylamino derivatives and the like. The vinylaromatic monomersmay be used at levels of from 0% to 50%, preferably 0% to 30% by weight,based on the total weight of the polymer of the composition of thisinvention.

Another class of suitable ethylenically unsaturated monomers that may beuseful as the at least one second monomer are nitrogen-containing ringcompounds and their thioanalogs, such as vinylpyridines such as2-vinylpyridine or 4-vinylpyridine, and lower alkyl (C₁-C₈) substitutedC-vinyl pyridines such as: 2-methyl-5-vinyl-pyridine,2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine,2,3-dimethyl-5-vinyl-pyridine, 2-methyl-3-ethyl-5-vinylpyridine;methyl-substituted quinolines and isoquinolines, N-vinylcaprolactam,N-vinylbutyrolactam, N-vinylpyrrolidone, vinyl imidazole, N-vinylcarbazole, N-vinyl-succinimide, acrylonitrile, o-, m-, orp-aminostyrene, maleimide, N-vinyl-oxazolidone, N,N-dimethylaminoethyl-vinyl-ether, ethyl-2-cyano acrylate, vinyl acetonitrile,N-vinylphthalimide. Also included are N-vinyl-thio-pyrrolidone, 3methyl-1-vinyl-pyrrolidone, 4-methyl-1-vinyl-pyrrolidone,5-methyl-1-vinyl-pyrrolidone, 3-ethyl-1-vinyl-pyrrolidone,3-butyl-1-vinyl-pyrrolidone, 3,3-dimethyl-1-vinyl-pyrrolidone,4,5-dimethyl-1-vinyl-pyrrolidone, 5,5-dimethyl-1-vinyl-pyrrolidone,3,3,5-trimethyl-1-vinyl-pyrrolidone, 4-ethyl-1-vinyl-pyrrolidone,5-methyl-5-ethyl-1-vinyl-pyrrolidone,3,4,5-trimethyl-1-vinyl-pyrrolidone, and other lower alkyl substitutedN-vinyl-pyrrolidones. The nitrogen-containing ring compounds and theirthioanalogs may be used at levels of from 0% to 50%, preferably 0% to30% by weight, based on the total weight of the polymer of thecomposition of this invention.

Another class of suitable ethylenically unsaturated monomers that may beuseful as the at least one second monomer are substituted ethylenemonomers, such as vinyl acetate, vinyl chloride, vinyl fluoride, vinylbromide, vinylidene chloride, vinylidene fluoride, vinylidene bromide,acrylonitrile, methacrylonitrile, acrylic acid (AA) and correspondingamides and esters, methacrylic acid (MAA) and corresponding amides andesters. The substituted ethylene monomers may be used at levels of from0% to 50%, preferably 0% to 30% by weight, based on the total weight ofthe polymer of the composition of this invention.

Another class of acrylic and methacrylic acid derivatives that may beuseful as the at least one second monomer is represented by substitutedalkyl acrylate and methacrylate and substituted acrylamide andmethacrylamide monomers. Examples include (meth)acrylates wherein thealkyl group is substituted with halogen, such as fluorine, chlorine orbromine; and nitro, cyano, alkoxy, haloalkyl, carbalkoxy, carboxy,amino, alkylamino derivatives, glycidyl (meth)acrylate and the like. Thesubstituted alkyl acrylate and methacrylate and substituted acrylamideand methacrylamide monomers may be used at levels of from 0% to 50%,preferably 0% to 30% by weight, based on the total weight of the polymerof the composition of this invention.

Each of the substituted monomers that may be useful as the at least onesecond monomer can be a single monomer or a mixture having differentnumbers of carbon atoms in the alkyl portion. The alkyl portion of eachmonomer can be linear or branched.

Hydroxyalkyl (meth)acrylate monomers may also be useful in thisinvention as the at least one second monomer. Among the hydroxyalkylmethacrylate and acrylate monomers suitable for use in the presentinvention are 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethylacrylate(HEA), 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethylmethacrylate, 2-hydroxy-propyl acrylate, 1-methyl-2-hydroxyethylacrylate, 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate. Thehydroxyalkyl (meth)acrylate monomers may be used at levels of from 0% to50%, preferably 0% to 30% by weight, based on the total weight of thepolymer of the composition of this invention.

Additional examples of substituted (meth)acrylate monomers useful as theat least one second monomer are those alkyl methacrylate and acrylatemonomers with a dialkylamino group in the alkyl radical, such asdimethylaminoethyl methacrylate, dimethylaminoethyl acrylate and thelike.

Other examples of substituted (meth)acrylate monomers useful as the atleast one second monomer are nitrogen-containing ring compounds(previously described) and dialkylaminoalkyl methacrylamide andacrylamide monomers, such as N,N-dimethylaminoethyl methacrylamide,N,N-dimethyl-aminopropyl methacrylamide, N,N-dimethylaminobutylmethacrylamide, N,N-diethylaminoethyl methacrylamide,N,N-diethylaminopropyl methacrylamide, N,N-diethylaminobutylmethacrylamide, N-(1,1-dimethyl-3-oxobutyl) acrylamide,N-(1,3-diphenyl-1-ethyl-3-oxobutyl) acrylamide,N-(1-methyl-1-phenyl-3-oxobutyl) methacrylamide, and 2-hydroxyethylacrylamide, N-methacrylamide of aminoethyl ethylene urea, N-methacryloxyethyl morpholine, N-maleimide of dimethylaminopropylamine and the like.

Ethylenically unsaturated acid monomers such as, for example acrylicacid, methacrylic acid, crotonic acid, phosphoethyl methacrylate,2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinyl sulfonate,itaconic acid, fumaric acid, maleic acid, monomethyl itaconate,monomethyl fumarate, monobutyl fumarate, and maleic anhydride may alsobe used as the at least one second monomer in the polymers of thisinvention. The ethylenically unsaturated acid monomers may be used atfrom 0%-20% by weight, based on the weight of the polymer.

The polymer of this invention can be linear, branched or partiallycrosslinked. It can be post crosslinkable. By post crosslinkable ismeant that the polymer may have reactive groups which do not reactduring polymerization, but may react after polymerization to providecrosslinking. The physical form of the polymer may be pellets, beads,emulsion, solution, or chunks. The polymer may have a molecular weightof from 5,000 to 5,000,000, preferably 10,000 to 2,000,000, morepreferably 20,000 to 1,000,000 as determined by gel permeationchromatography (“GPC”). The polymer may have a melting point of from 20°C. to 110° C. as determined by differential scanning calorimetry(“DSC”). Alternate processes may be used to prepare the polymer of thisinvention. Suitable processes include solution polymerization, aqueoussuspension polymerization, and aqueous dispersion polymerization (bothbatch and semi-continuous).

In the slurry process of the invention, a slurry is formed by cooling asolution containing the SWM and a solvent until the SWM precipitates outof solution as crystals. This process may be used for solution orsuspension polymerization. For a solution process embodiment, the SWMmay be admixed with an organic solvent and heated until the SWM ismelted and dissolved, and then cooled with agitation. Suitable solventsinclude, but are not limited to hexane, heptane, xylene, toluene, ethylacetate, butyl acetate, hexanol, heptanol, octanol, decane, decalin, andthe like. After cooling, other monomers may be added. Suitable monomersinclude (meth)acrylic acid, esters of (meth)acrylic acid, (meth)acrylicamides, vinyl aromatic monomers, substituted ethylene monomers,functional monomers with a post crosslinkable group, multifunctionalmonomers, and mixtures thereof. The cooled slurry can be gradually addedto a reaction kettle in the presence of an initiator to form solutionpolymers.

For a suspension process embodiment, the SWM may be admixed with othermonomers and an aqueous solution and heated until the SWM is melted anddissolved in the organic phase. The mixture is cooled below thetemperature at which polymerization will be initiated and then initiatoris added. The mixture is stirred to evenly incorporate the initator intothe organic phase. The cooled mixture containing the initiator is thenheated and the stirring rate is increased to form a dispersion and toinitiate polymerization. The aqueous solution may contain a suspendingagent/dispersant for stabilizing polymerizing droplets. The suspendingagent/dispersant may be used at from 0.01% to 5% by weight, based on thetotal weight of the mixture. Suitable suspending agents/dispersantsinclude polyalkyldimethylammonium chloride, polyvinylalcohol,hydroxyethylcellulose, hydroxypropylcellulose or various other cellulosematerials, polyvinyl pyrrolidone, natural gum, powdered dispersants, andthe sodium salt of poly(meth)acrylic acid homopolymer or copolymers.

In the dispersion process of the invention, a solution containing a SWMin at least one second monomer is provided. In the process, the solutionmay be obtained by heating an admixture of a SWM in at least one secondmonomer until the synthetic wax monomer melts and dissolves as describedabove. The solution may be admixed with a second aqueous surfactantsolution to create a monomer emulsion.

In one embodiment of the dispersion process, the at least one secondmonomer of the first solution may be selected from the monomersdescribed above, including (meth)acrylic acid, esters of (meth)acrylicacid, (meth)acrylic amides, vinyl aromatic monomers, substitutedethylene monomers, functional monomers with a post crosslinkable group,multifunctional monomers, and mixtures thereof.

In a second embodiment of the dispersion process, the at least onesecond monomer of the first solution may be selected from a SWMcontaining polyethylene blocks. In this case, the second SWM acts as anaqueous dispersant for the first SWM. SWMs such aspoly(ethylene-b-ethyleneoxide)-acrylate (Unithox™ 450 acrylate), may besuitable for these purposes. Similar low molecular weight diblockpolymers without the polymerizable (meth)acrylate end group, such aspoly(ethylene)-b-poly(ethyleneoxide)-OH (Unithox™ ethoxylate), may alsobe used as dispersants. The dispersants may be used at from 0% to 20% byweight, preferably 1% to 15% by weight, more preferably 2% to 10% basedon the total weight of the first synthetic wax monomer.

For both dispersion process embodiments, the second solution may be anaqueous surfactant solution. Surfactants may be used at from 0.1% to 5%by weight, based on the total weight of the monomer mixture. Thesurfactants can be anionic, nonionic or cationic. Anionic surfactants ora combination of an anionic surfactant with a nonionic surfactant arepreferred.

In the processes of the invention, a reaction mixture is formed byadmixing at least one second monomer with the SWM. The amount of the atleast one second monomer admixed with the SWM ranges from 50% to 99%,preferably 60% to 97%, more preferably 65% to 95% by weight based on theweight of the SWM. The at least one second monomer to be admixed withthe synthetic wax monomer may be selected from the monomers describedabove, including (meth)acrylic acid, esters of (meth)acrylic acid,(meth)acrylic amides, vinyl aromatic monomers, substituted ethylenemonomers, functional monomers with a post crosslinkable group,multifunctional monomers, and mixtures thereof.

In the processes of the invention, the monomers may be polymerized byco-feeding the reaction mixture and an initiator to a reactor or batchpolymerizing a reaction mixture in a reactor at a temperature sufficientto initiate polymerization. Typically, the reactor is at a temperaturefrom 75° C. to 110° C. The initiator is preferably water insoluble andmay be selected from peroxyesters, dialkylperoxides,alkylhydroperoxides, persulfates, azoinitiators, redox initiators andother known free radical inititators. Part of the initiator isincorporated into the polymer as end groups. The amount of the initiatorused is generally from 0.05% to 5% by weight, based on the weight oftotal monomer.

The dispersion process will yield a latex polymer. The polymer from thelatex can be isolated by any method known in the art, such as spraydrying, freeze drying, or coagulation. The suspension process will yieldpolymer beads. The polymer beads can be isolated by filtration. Thesolution process will yield a homogeneous polymer solution when a goodsolvent is used. Toluene, xylene, and decalin are examples of goodsolvents. If one wants to isolate the polymer from solution, one woulduse a poor solvent. By poor solvent is meant that the polymer is solublein the solvent at high temperature, but insoluble at low temperature.Examples of poor solvents are heptane, hexane, or other saturated alkanesolvents. The polymer may be isolated by cooling of the solutionfollowed by filtration. Where a solid is isolated, the solid may containsolvent and may be vacuum dried at ambient temperature to give neatpolymer chunks. The crumbly solid may also be diluted in solvent,re-heated to form a solution, cooled with stirring, vacuum filtered, andair dried on a Buchner funnel to yield solid polymer chunks.

Chain transfer agents may be used for regulating molecular weight in theprocesses to prepare the polymers of this invention. Suitable chaintransfer agents include organic thiol compounds such as n-dodecylmercaptan and the like. The chain transfer agent may be used at 0% to10% by weight of the total monomer mixture. When used in the processesto prepare the polymers of this invention, part of the chain transferagent structure is incorporated into the polymer as an end group.

A salt may be used in suspension processes of preparing the polymers ofthis invention to reduce the solubility of organic monomers in theaqueous phase. The salt may be used at from 0% to 8% by weight, based onthe total weight of the mixture. Suitable salts include sodium chloride,potassium chloride and the like.

Organic solvents may be used in suspension processes of preparing thepolymers of this invention for improving the solubility of the syntheticwax (meth)acrylate in the other monomers. The organic solvents may beused at from 0% to 200% by weight, preferably 0% to 100% by weight,based on the total weight of the synthetic wax (meth)acrylate.

A buffer may be useful in dispersion processes to prepare the polymersof this invention to maintain the pH of the aqueous phase. Suitablebuffers include sodium, potassium, and ammonium salts of carbonate,bicarbonate, acetate, phosphate, and borate. The buffers may be used atfrom 0% to 5% based on the total weight of the composition.

Sodium nitrite or sodium perborate may be useful as radical inhibitorsin dispersion processes to prepare the polymers of this invention toinhibit any undesirable polymerization in the aqueous phase. The radicalinhibitors may be used at from 0% to 1% based on the total weight ofwater in the composition.

The polymers prepared by the process of the invention are useful inapplications such as hot melt adhesives, hot melt sealants/caulks,plastic additives, compatibilizers, textile binders, roof mastics,traffic paints, barrier or protective coatings, powder coatings, waterresistant sealer for wood and masonry materials, floor wax, waterrepellants for textiles, carrier polymers of biocides or other activeingredients in agriculture products.

For use in the above coating applications, the polymer may be formulatedwith materials such as binders, pigments, additives and fillers toprepare coating compositions suitable for each application. The coatingcomposition is then applied to a substrate and then dried. The coatingcomposition may be applied by spraying, dipping, or other methods knownin the art. Suitable substrates include vinyl, polypropylene, metal,wood, cement, paper, nonwovens, textiles, and other substrates known inthe art. The coating composition may be dried under ambient conditions.Forced air may be utilized to aid in the drying of the coatingcomposition. Heat may also be utilized in the drying of the coatingcomposition. The forced air may be heated, or the coated substrate maybe placed in a heated oven. The temperature of the heat may range from35° C. to 110° C.

The polymers of this invention may also be useful as dry powder coatingcompositions. For dry powder coating compositions, the polymer isisolated as a solid by the techniques described above. The dry polymermay be ground to a powder by any milling equipment suitable forproducing particles in the size range of 0.1 to 50 microns, morepreferably 0.25 microns to 35 microns, and most preferably from 0.5microns to 25 microns. The particle size may be measured on a Coulter™LS, light scattering, particle size analyzer. Suitable mills areattrition mills, fluid-energy mills, colloid mills, vibratory ball mills(vibro-energy mills), pin mills, ball mills, roller mills, andautogenous and semiautogenous mills. Likewise a combination of millscould be used to possibly increase speed where the first mill reducesparticle size to, for example, 100 to 1000 microns and a second millreduces the particle size further to the desired range. An example wouldbe the initial use of a hammer mill followed by a semiautogenous milllike a Dyno-Mill™ from CB Mills Inc (Buffalo Grove, Ill.).

The dry powder may be applied to a substrate, heated to form a film, andcooled. Suitable substrates include vinyl, polypropylene, metal, wood,cement, paper, nonwovens, textiles, and other substrates known in theart. The dry polymer powder may be heated at temperatures ranging from60° C. to 150° C. to form a film. The film may then be cooled either bystorage at ambient temperature or by the use of cooled forced air.

The polymer may also be useful as an adhesive. For adhesiveapplications, a first polymer coated substrate is formed by applying thepolymer to a substrate such as vinyl, polypropylene, metal, wood,cement, or paper. The polymer may be in the form of a liquid or a solid.For a solid polymer, the polymer is then heated to the melting point ofthe polymer. A second substrate may then be applied to the first polymercoated substrate. The second substrate may be selected from vinyl,polypropylene, metal, wood, cement, paper, or release paper. The polymeris then dried or cooled. The polymer may be dried under ambientconditions. Forced air may be utilized to aid in the drying of thecoating composition. Heat may also be utilized in the drying of thecoating composition. The forced air may be heated, or the coatedsubstrate may be placed in a heated oven. The temperature of the heatmay range from 35° C. to 110° C. The polymer may be cooled either bystorage at ambient temperature or by the use of cooled forced air.

The following examples are intended to demonstrate the polymer of theinvention, the process of the invention, alternate processes to preparethe polymer of the invention, and the usefulness of the polymer of theinvention in various applications. The following abbreviations applythroughout the examples:

SWM 1=Unilin™ 550MA (C₄₀ (average) methacrylate)

SWM 2=Unilin™ 550A (C₄₀ (average) acrylate)

SWM 3=Unilin™ 700MA (C₅₀ (average) methacrylate)

SWM 4=Unilin™ 700A (C₅₀ (average) acrylate)

SWM 5=Unilin™ 350A (C₂₅ (average) acrylate)

SWM 6=Unilin™ 350MA (C₂₅ (average) methacrylate)

SWM 7=Unilin™ 425A (C₃₅ (average) acrylate)

SWM 8=Behenyl Acrylate

SWM 9=Unithox™ 450A (C₃₀ (average)-b-(CH₂CH₂O)_(10.5) (average)acrylate)

SWM 10=Unithox™ 450MA (C₃₀ (average)-b-(CH₂CH₂O)_(10.5) (average)methacrylate)

DISP 1=Unilin™ 450 ethoxylate

DISP 2=Unilin™ 550 ethoxylate

IBOMA=isobornyl methacrylate

Preparation of Polymer Using Process 1 (Solution/Slurry)

A mixture of 75.0 grams of SWM 4 and 131.3 grams of heptane was heatedto form a solution. The solution was stirred magnetically and allowed tocool. During cooling, SWM crystals precipitated from the solution. Whenthe temperature had dropped to 50° C.-60° C. there was added 150.0 gramsof butyl acrylate. The solution temperature dropped to 40° C. Onehundred fifty grams of methyl methacrylate was then added to thesolution. The temperature of the solution dropped to 30° C. The mixturewas allowed to cool to room temperature to give an easily stirrableslurry. An initiator solution was prepared using 6.3 grams of Lupersol575 (t-amylperoxy 2-ethylhexanoate) and 26.6 grams of heptane.

A 25.3 gram portion of the monomer slurry and 39.2 grams heptane wereweighed into a 1-liter 4-necked flask fitted with a C-stirrer,thermocouple, N₂ inlet, and separate feed lines for monomer-slurry andinitiator solution. This mixture was stirred with a N₂ blanket andheated until a gentle reflux began at approximately 85° C. A 2.1 gramportion of the initiator solution was then added. A clear, pale yellowsolution resulted. After a ten minute hold, simultaneous feeds ofmonomer slurry and initiator solution were begun and enough heat wasapplied to maintain gentle reflux of the solution. After three hours atotal of 269.1 grams of the monomer slurry had been fed and thetemperature had reached 102° C. Both feeds were stopped for 15 minutes,then the remainder of the initiator solution was fed over 25 minutes.Following a 15 minute hold, the mixture was allowed to cool to roomtemperature. The polymer crystallized to give a crumbly solid which was65% polymer, 35% heptane. A portion of this solid was vacuum dried atambient temperature to give neat polymer chunks. Alternatively, aportion of the 65% solid material was diluted to approximately 30%solids with additional heptane, reheated to form a clear solution, thencooled to 7° C. with stirring, vacuum filtered and air dried on aBuchner funnel to give solid polymer chunks similar to those obtained byvacuum drying the 65% solid material.

Preparation of Polymer by Process 2 (Suspension Polymerization)

To 0.75 gram NaH₂PO₄.2H₂O in a 500 ml 4-neck flask was added 100.0 gramsdeionized water and 3.75 grams of a 22.5% aqueous solution of dispersantEM-2B (methacrylic acid copolymer sodium salt) to give a clear solutionpH 6.7. To the clear solution was then added 32.0 grams of butylmethacrylate and 10.0 grams of SWM 1. This mixture was stirred slowlywith a N₂ sweep and heated to gentle reflux until the SWM 1 melted anddissolved to make a nearly clear solution, then cooled to 56° C. Asolution of 0.53 grams of 95% Lupersol 575 in 8.0 grams of butylmethacrylate was then added. The stirring rate was increased and themixture reheated to 95° C. over 10 minutes. The solution was stirred atthat temperature for 2 hours, then allowed to cool. The polymer beadswere collected by filtration, rinsed with deionized water, and allowedto dry at room temperature.

Characterization of the beads: The percent solids (30 minutes @ 150° C.)was 99.1 (average). The actual yield of polymer solids was 48.9 grams or97.7% of theory. The residual acrylic monomer was 2969 ppm BMA asdetermined by Gas Chromatography (“GC”). The portion of the polymersolids soluble in tetrahydrofuran at room temperature was 78%. The beadsflowed together to form a film when heated at 150° C. DSC of the polymershowed a Glass Transition Temperature (“Tg”) of 28° C. and a single melttemperature of 67° C. The latter was an indication that the SWM wasevenly incorporated into the acrylic polymer.

Preparation of Polymer by Process 3 (Solution)

A 1 liter reaction vessel was fitted with a thermocouple, a temperaturecontroller, a purge gas inlet, a water-cooled reflux condenser withpurge gas outlet, a stirrer, an Insta-Therm jacketed addition funnel,and a non-jacketed addition funnel. To the non-jacketed addition funnelwas fed Monomer Mix ‘A’ which contained 316.34 grams of a homogeneousmixture of 122.50 grams butyl acrylate (100% purity), 192.76 gramsmethyl methacrylate (99.85% purity), 0.70 grams Lupersol 575, and 0.35grams dodecyl mercaptan. To the jacketed addition funnel which washeated to and maintained at 90° C. to 100° C. was fed Monomer Mix ‘B’which contained 56.88 grams of a homogeneous mixture of 43.76 grams SWM4 (80.0% purity), and 17.50 grams toluene.

Ten percent (31.63 grams) of Monomer Mix ‘A’, 10 percent (6.13 grams) ofMonomer Mix ‘B’, and 87.50 grams toluene were fed to the reaction vesselwhich was then flushed with nitrogen for 30 minutes before applying heatto bring the contents of the reaction vessel to 95° C. When the contentsof the vessel reached 95° C., the balance of both Monomer Mix ‘A’ and‘B’ were uniformly fed to the reaction vessel over 60 minutes. At theend of the monomer mixture addition, the reaction vessel contents weremaintained at 95° C. for 30 minutes. At the end of the 30 minute hold,the polymerization temperature was increased to 100° C. before startinga feed which contained 1.40 grams of Lupersol 575 and 35.00 gramstoluene. The feed was added uniformly over a 60 minute period. At theend of the feed the batch was held at 100° C. for 60 minutes. At the endof the 60 minute hold, vacuum was applied and toluene was removed fromthe batch. The batch was eventually subjected to a vacuum of 25 mm Hg at120° C. for 1 hour. The product so formed exhibited a polymer solidscontent of 97.8 weight % (by GPC), and a molecular weight (Mw) of341,000.

Preparation of Polymer by Process 4 (Batch Dispersion Polymerization)

SWM 2 (25 grams) was dissolved in 75 grams styrene at 80° C. to 85° C.After the solution became uniform, 150 grams butyl acrylate, preheatedto 80° C., was added to the solution. The mixture was agitated to keepit uniform. In a separate container, 200 grams deionized water and 2.5grams of a 60% surfactant aqueous solution of Rhodapex CO436 were heatedto 90° C. The monomer solution was added to the water/surfactantsolution and homogenized at 15,000 rpm for several 30 seconds on-offcycles until the monomer emulsion turned thick.

While preparing the above monomer emulsion, 800 grams of deionized waterwas heated to 80° C. in a 3-liter round bottom flask with a condenser, athermocouple, a mechanical stirrer and a nitrogen gas inlet, to providea positive pressure of nitrogen flow in the head space of the reactor.The hot monomer emulsion was poured into the reactor followed byaddition of 0.7 gram t-butylperoctoate. The reaction mixture was kept at80° C. for 4 hours while agitated. At the end of the reaction, themixture was cooled to room temperature.

Preparation of Polymer by Process 5 (Semi-Continuous DispersionPolymerization)

SWM 5 (60 grams) and polyethylene-b-polyethyleneoxide dispersing aidDISP 1 (6 grams) were mixed together and heated until melted. Underagitation a mixture consisting of 528 grams butyl acrylate, 12 gramsmethacrylic acid and 3 grams n-dodecyl mercaptan was then added to theSWM 5 and DISP 1 mixture. The solution was heated at 85° C. and stirreduntil uniform. In a separate container, 600 grams deionized water and21.4 grams of a 28% surfactant (sodium lauryl sulfate) aqueous solutionwere heated to 90° C. The hot monomer solution and the hot watersurfactant solution were mixed and homogenized at 15,000 rpm for several30 seconds on-off cycles until the monomer emulsion turned thick. Afterthe monomer emulsion was cooled to below 40° C. under gentle stirring, 2grams of t-butylperoctoate was added to the monomer emulsion and stirredfor at least 10 minutes.

While preparing the above monomer emulsion, 200 grams deionized waterwas heated to 85° C. in a 3-liter round bottom flask with a condenser, athermacouple, a mechanical stirrer and a nitrogen gas inlet, to providea positive pressure of nitrogen flow in the head space of the reactor.Half of the monomer emulsion was added to the reactor. The mixture wasallowed to react for 30 minutes. Then the second half of the monomeremulsion was gradually added into the reactor through a pump into thereactor in 2 hours. After the completion of the monomer emulsion feed,the reaction mixture was held at 85° C. for 1 hour and then cooled toroom temperature.

The following were prepared by the processes described above:

Process Sample Composition Made By  1 1 DISP 1/2 MAA/88 BA/10 SWM 5 5  21 DISP 1/2 MAA/88 EHA/10 SWM 5 5  3 1 DISP 2/29 IBOMA/2 MAA/59 BA/10 SWM2 5  4 30 Sty/60 BA/10 SWM 1 4  5* 33 Sty/67 BA 4  6 30 Sty/59 BA/1MAA/10 SWM 1 4  7 15 Sty/73 BA/2 MAA/10 SWM 1 4  8 40 Sty/5 MMA/10 BA/5MAA/40 SWM 2 4  9 25 Sty/30 MMA/ 20 BA/ 25 SWM 2 4 10 26 Sty/52 BA/2MAA/20 SWM 2 4 11 20 Sty/58 BA/2 MAA/20 SWM 2 4 12 29 Sty/59 BA/2 MAA/10SWM 9 4  13* 88.9 BA/ 11.1 AA 3 H 14 80 BA/10 MAA/10 SWM 1 3 H 15 80BA/10 MMA/10 SWM 1 3 H 16 78 BA/10 MMA/2 AA/10 SWM 1 3 H 17 83 BA/10MMA/2 AA/5 SWM 1 3 H 18 83 BA/10 MMA/2 AA/5 SWM 3 3 H 19 83 BA/10 MMA/2AA/5 SWM 10 3 H 20 83 BA/10 MMA/2 AA/5 SWM 6 3 H  21* 40 BA/60 MMA 3 22* 35 BA/65 MMA 3  23* 30 BA/70 MMA 3  24* 25 BA/75 MMA 3 25 40 BA/55MMA/5 SWM 4 3 26 35 BA/60 MMA/5 SWM 4 3 27 30 BA/65 MMA/5 SWM 4 3 28 50BA/40 MMA/10 SWM 4 3 29 45 BA/45 MMA/10 SWM 4 3 30 40 BA/50 MMA/10 SWM 43 31 35 BA/55 MMA/10 SWM 4 3 32 30 BA/60 MMA/10 SWM 4 3 33 50 BA/30MMA/20 SWM 4 3 34 45 BA/35 MMA/20 SWM 4 3 35 40 BA/40 MMA/20 SWM 4 3 3635 BA/45 MMA/20 SWM 4 3 37 30 BA/50 MMA/20 SWM 4 3  38* 40 BA/60 SWM 4 3 39* 40 BA/60 SWM 2 3  40* 40 BA/60 SWM 7 3  41* 40 BA/60 SWM 5 3 42 60BA/40 SWM 7 3 43 60 BA/40 SWM 5 3 44 80 BA/20 SWM 7 3 45 80 BA/20 SWM 53  46* 45 BA/55 MMA 3 47 47 BA/43 MMA/10 SWM 1 3 H 48 10Sty/33MMA/47BA/10 SWM 2 4  49* 40 BA/60 SWM 8 3 50 60 BA/40 SWM 8 3 5180 BA/20 SWM 8 3 52 90 BA/10 SWM 8 3 53 90 BA/10 SWM 5 3 54 90 BA/10 SWM7 3 55 80 BMA/20 SWM 1 2 56 80 BMA/20 SWM/1 nDDM 2 57 60 BMA/40 SWM 1 258 60 BMA/40 SWM 1/1 nDDM 2 59 60 BMA/40 SWM 1/2 nDDM 2 *ComparativeExample SWM = synthetic wax monomer H = heptane substituted for toluene,reaction run at 90° C.

Adhesive Testing

An ASTM Tape Test was used to determine adhesion (D 3359-90). Thesubstrates were thermoplastic polyolefin (TPO): Dexter D/S 756-67 andpolypropylene (PP): Himont SB 823. Plaques were wiped gently withisopropanol. Samples were drawndown using a wire-wound rod, then heatedat 50° C. for 30 minutes. The samples were dried in a constanttemperature room for 1 week prior to testing for adhesion. The resultsare shown in Table 1.

TABLE 1 Sample TPO PP 47 5 4.5  5* 0 1  6 2 2

The data above shows the polymers of the invention are useful asadhesives, even on substrates where good adhesion is normally difficultto obtain.

Water Repellents for Nonwovens and Textiles

Polymer compositions of this invention were used as binders informulations for treating fabric. The polymers were added to theformulations at 10% by weight. The formulations were padded on a BirchBrothers padder at a pressure of 0.17 MPa and a speed of 8 meters perminute. The binder add-on was 6% by weight. The samples were dried in aMathis oven at 150° C. for 4 minutes.

The dried samples were evaluated using AATCC Test Method 22-1980 WaterRepellency Spray Test. The results are shown in Table 2.

TABLE 2 Sample Rating Control (No Formulation Padded) 0 48 80 11 70

The data above indicate that the polymers of this invention are usefulas water repellents in nonwoven and textile applications.

Wax Replacement in Floor Polish Testing

The following floor polish formulation was used to test the polymercomposition of the invention. The acrylic binder/alkaline swellableresin/wax ratio in this formulation is 75/10/15. Equal weight of thepolymer composition of the invention was substituted for commercialwaxes Epolene®E-43N and Poly Emulsion®325N35. For the no wax controlsample, the Rhoplex 1421 level was increased on an equal weight basis toaccount for the removal of Epolene®E043N and Poly Emulsion®325N35.

Material In Order Of Addition Percent by Weight Water 30.73Kathon ®CG/ICP 0.03 Acrysol ®644 (42%) 5.52 Fluorad ® FC-129 (50%) 0.02Diethylene Glycol Ethyl Ether 5.78 Tripropylene Glycol Methyl ether 1.02Rhoplex ®1421 (38%) 45.76 Epolene ® E-43N (40%) 4.35 Poly Emulsion324N35(35%) 4.97 SE-21 0.02

The floor polish was coated on black vinyl (B.V.) for the lab gloss testand on black vinyl composition tile (B.V.C.) for lab black heel mark andscuff tests. The floor test was done on commercial vinyl floor tiles.

Black Heel Mark and Scuff Resistance Test: The lab test is described inChemical Specialty Manufacturers Association Bulletin No. 9-73 withrubber shoe heels substituted in place of rubber cubes. The Rating scalewas 1-10 with 10 being best performance. The floor test was evaluated onmarks made by pedestrian traffic in commercial buildings.

Static Coefficient Of Friction (S.C.O.F.): The S.C.O.F. was determinedby the James Friction Testing Machine based on an average of fourreadings.

Gloss was determined by the ASTM D1455 method.

The results of the tests described above are shown in Tables 3 and 4.

TABLE 3 Sample Particle Size Gloss Black Mark Scuff S.C.O.F. 4 257 10/416 4, light 0.83 PE Wax* 150 16/49 8 7 0.54 NO Wax* NA 18/52 6 5 0.90 PEWax/No Wax = comparative examples NA = not analyzed

TABLE 4 Sample P.S B.V. B.V.C. Black Mark Scuff S.C.O.F. 12 240 69/8919/49 5 6 0.78 11 375 39/73 11/41 8, light 7 0.72 9 326 18/42  7/29 5 90.77 10 351 16/44  7/30 5, light 6 0.74 8 418  9/31  3/17 6 9 0.74 PE*150 76/90 19/49 9 8 0.64 P.S. = particle size (nm) B.V. = black vinylgloss 20°/60° B.V.C. = black vinyl composition gloss 20°/60°*comparative example

Samples 4, 11 and 12 were further tested in a high traffic hallway whichwas burnished with an UHS Tan Buffer Pad on a 2000 rpm propane floorburnishing machine periodically. The results are shown in Tables 5 and6.

TABLE 5 Sample I.G. Burn. 1 week 2 weeks 3 weeks Scuff B.M. 4 21/65 6426/46 47/73 54/55 8 9 PE* 30/69 91 23/34 27/68 42/51 9 8 I.G. = initialgloss 20°/60° Burn. = burnished gloss 20°/60° 1 week = 20° gloss asis/burnished 2 weeks = 20°/60° gloss burnished 3 weeks = 20° glossburnished 1 pass/4 passes B.M. = black mark

TABLE 6 Sample I.G. Burn. 1 week 1 week* 2 weeks 2 week* Scuff 12 8 8753 6 9 10 8/7 11 5 (hazy) 64 26 7 9 16 8/7 PE* 9 91 54 8 9 12 9/8 I.G. =initial gloss 20°/60° Burn. = burnished gloss 20°/60° 1 week = 20°/60°gloss 1 week* = 20°/60° gloss burnished after 1 week 2 weeks = 20°/60°gloss after 2 weeks 2 weeks* = 20°/60° gloss burnished after 2 weeksScuff = scuff after 1 week/2 weeks

The data above demonstrates that the compositions of this inventionresponded well to floor burnishing due to their crystallinity.

Dry Powder Coatings

The polymer compostions of this invention were tested for usefulness asdry powder coating compositions. The polymers were ground using aScienceWare Micro Mill™ grinder. One gram of each dry polymer powder wasplaced in an aluminum weighing pan. The rest of the dry polymer powderwas stored in a jar at room temperature. The room temperature sampleswere checked to see if they remained free flowing powders after 24 hoursstorage. The samples in the weighing pans were placed in ovens at 120°C., 140° C., and 150° C. to determine at what temperature and time wouldthe dry polymer powder form a film. For dry polymer powder coatings, afilm forming temperature in the range of 120° C. to 150° C. isacceptable, but the time to form a film is preferably less than 3 hours.The powder stability and time to form a film results are shown in Table7.

TABLE 7 Powder Sample Stability 120° C. 140° C. 150° C. 21* S  >3 hours 2.5 hours NT 22* Good  >3 hours  2.5 hours NT 23* Good  >3 hours   >3hours 2.5 hours 24* Good  >3 hours   >3 hours 2.5 hours 25 Good  >3hours   >3 hours 2.5 hours 26 Good  >3 hours   >3 hours 2.5 hours 27Good  >3 hours   >3 hours  >3 hours 28 S <0.5 hours NT NT 29 Good   1hour NT NT 30 Good  1.5 hours NT NT 31 Good  >3 hours 1.25 hours NT 32Good  >3 hours   >3 hours 2.5 hours 33 Good 0.75 hours NT NT 34 Good0.75 hours NT NT 35 Good 0.75 hours NT NT 36 Good 1.75 hours NT NT 37Good 1.75 hours NT NT 38 Good <0.5 hours NT NT 39 Good <0.5 hours NT NT40 Good <0.5 hours NT NT 41 Good <0.5 hours NT NT 42 Good <0.5 hours NTNT 4a T NT NT NT 44 T NT NT NT 45 T NT NT NT 55 G NT NT <0.5 hours 56 SNT NT <0.5 hours 57 G NT NT <0.5 hours 58 G NT NT <0.5 hours 59 G NT NT<0.5 hours Good = free flowing powder after 24 hours storage S =slightly tacky, not as free flowing as Good T = tacky, did not form adry polymer powder NT = not tested *comparative example

The data above indicates that the polymers of this invention are usefulas dry powder coating compositions.

Some of the properties of the polymers of this invention were comparedto polymers with greater than 50 percent by weight synthetic wax monomerincorporation. The data are shown in Table 8.

TABLE 8 Sample/Rating SWM/BA C₂₀ C₂₅ C₃₅ C₄₀ C₅₀ 60/40 49/P 41/P 40/P39/P   38/P 40/60 50/T 43/S 42/P 57/P* NT 20/80 51/T 45/T 44/S 55/P* NT10/90 52/T 53/T 54/T NT NT SWM/BA = weight ratio of synthetic waxmonomer to butyl acrylate P = stable powder, no tack, film formation at120° C. *film formation tested at 150° C. T = tacky, can not make powderS = slightly tacky, hard to make powder NT = not tested

The data above demonstrates that polymers with greater than 50 percentby weight synthetic wax monomer incorporation form dry powders and arenon-tacky regardless of the length of the carbon chain on the syntheticwax monomer. The synthetic wax monomer is significantly more expensivethan butyl acrylate and other monomers incorporated in the polymers ofthis invention. Therefore, it is desirable to reduce the amount ofsynthetic wax monomer below 60 percent by weight without sacrificing thedry powder polymer properties. The data above shows that the dry powderpolymer properties at 60 percent synthetic wax monomer incorporation maybe retained at 40 percent incorporation by increasing the length of thecarbon chain on the synthetic wax monomer. The data suggests that it maybe possible to reduce the percent incorporation of synthetic wax monomerto between 10 and 20 percent by weight without sacrificing dry powderpolymer properties.

Hot Melt Sealant

The polymer compositions of this invention were tested as hot meltsealants by applying the solid polymers to glass and vinyl substrates.The samples were heated in an oven to 80° C., 90° C., and 115° C. Theheated polymers were checked to see how well they melted at eachtemperature. A nylon screen was applied over each melted polymer. Thepolymer was cooled and tested for adhesion with an Instron machinepulling the screen away from the polymer coated substrate. The resultsare shown in Table 9.

TABLE 9 Melt Behavior Adhesion (kg/m) Sample 80° C. 90° C. 115° C. GlassVinyl  13* Poor Poor Poor NT NT 14 Poor Poor Partial 214-321 C A 15Partial Good Good 5 A C 16 Partial Partial Good 18-36 A A 17 PartialGood Good 125-143 C C 18 Poor Partial Good 179-250 C A/C 19 PartialPartial Good NT C 20 Good Good Good 71 A A NT = not tested A = adhesivefailure C = cohesive failure *comparative example

The data above indicate that the polymers of this invention are usefulas hot melt sealants.

Wood Treatment

The polymer compositions of this invention were applied to wood boardsand tested for utility as water repellents for wood applications.Matched sapwood boards measuring 1.8 cm×1.8 cm×1.8 cm(tangential×radial×logitudinal) were used for this test. The wood wasstraight grained, flat sawn, clear with 6 to 10 rings per 2.5 cm, and40% to 50% summerwood. Samples were cut with a fine tooth saw to obtainas smooth a surface as possible. The polymer compositions and controlwood treatment compositions were applied to the wood boards by pressuretreatment. For each level (weight percent) of coating compositiontested, two wood boards were coated with the polymer of this invention.The coated wood was dried for two weeks.

Samples were conditioned for 10 days at 45% relative humidity. Thesample weights were checked until constant to insure moistureequilibrium. Samples were weighed to the nearest 0.001 grams. Sampleswere tested using a Dynamic Swellometer apparatus that records swell inthousands of an inch. The instrument automatically measures Swell Valuesduring the test. Samples were measured (radial, tangential, longitudinaldimensions) using a micrometer and the measurements were recorded.Samples were placed radially in a swell chamber and secured so that nofloating could occur during testing. Samples were then covered withdistilled water and tested for 100 minutes. Immediately after testing,the samples were removed and weighed to the nearest 0.001 gram. Sampleswere again measured (radial, tangential, longitudinal dimensions) usinga micrometer and the measurements were recorded.

Water Repellency Efficiency (“WRE”) was measured following the followingformula: ${\% \quad {WRE}} = {\frac{A - B}{A} \times 100}$

A=10 or 100 minute Control Swell Value

B=10 or 100 minute Polymer Of Invention Swell Value

The first wood board was sampled 4 times. The second wood board wassampled 2 times. The results of the tests were averaged. The results areshown in

TABLE 10 Average % WRE Coating Level (Weight %) 10 Minutes 60 MinutesWax* 0.6 87 51 CCA/Wax* 0.6/0.6 83 53 4 1 72 41 2.5 91 59 5 82 44 7 1−32$ −37$ 2.5 77 35 5 93 70 *comparative example CCA = copper chromearsenate $ = experimental error suspected

The data above shows that the polymers of this invention provide goodwater resistance and are suitable for wood treatment applications.

We claim:
 1. A method of using a polymer as an adhesive comprisingapplying said polymer to a substrate to form a first polymer coatedsubstrate, then applying a second substrate to said first polymer coatedsubstrate wherein said polymer is prepared by, first, forming a slurryby cooling a solution which contains a solvent and from 1 to less than50 percent by weight of a synthetic wax monomer of formula I:

wherein R1 is selected from H and CH3, R2 is selected from H and C1-C5alkyl, R3 is selected from H and CH3, n=9-115, and m=0-1370; second,adding from 50 to 99 percent by weight of at least one second monomer;and finally, polymerizing the reaction mixture in the presence of aninitiator.